O-(2-vinyl phenyl) thiolphosphates

ABSTRACT

Compounds of the formula   WHEREIN R1 represents methyl or ethyl, R2 represents n-propyl, isopropyl, isobutyl, sec. butyl or n-amyl, R3 represents hydrogen or methyl, X represents hydrogen, halogen, methyl, methylthio, methylsulphinyl, methoxy or acetyl, and n is 1 to 3, and their use for controlling insects, representatives of the order Acarina, phytopathogenic fungi and phytopathogenic nematodes are disclosed.

United States Patent [1 1 Boger et al.

[ Aug. 5, 1975 1 O-(Z-VINYL PHENYL) THIOLPHOSPHATES [75] Inventors:Manfred Boger, Haltingen,

Germany; Jozef Drabek, Allschwil,

[21] Appl. No.: 449,416

[30] Foreign Application Priority Data Mar. 15, 1973 Switzerland 3776/73Jan. 30, 1974 Switzerland 1261/74 [52] US. Cl. 260/956; 260/946;260/949;

260/951; 424/214; 424/216; 424/217; 424/219 [51] Int. Cl C07f 9/16; AOln9/36 [58] Field of Search 260/956 [56] References Cited UNITED STATESPATENTS 2,275,041 3/1942 Britton ct a1 260/956 Primary Examiner-Anton H.Sutto Attorney, Agent, or FirmFrederick H. Rabin [57] ABSTRACT Compoundsof the formula wherein R represents methyl or ethyl, R representsn-propyl, isopropyl, isobutyl, sec. butyl or n-amyl, R representshydrogen or methyl, X represents hydrogen, halogen, methyl, methylthio,methylsulphinyl, methoxy or acetyl, and n is 1 to 3, and their use forcontrolling insects, representatives of the order Acarina,phytopathogenic fungi and phytopathogenic nematodes are disclosed;

9 Claims, No Drawings 1 O-(Z-VINYL PHENYL) THIOLPHOSPHATES The presentinvention provides thiolphosphoric acid esters, a process for theirmanufacture, and a method of using them in pest control.

The thiolphosphoric acid esters have the formula f3 0 cH=ccH 1 L (I) 11s 0 R n 1b) PCl wherein R represents methyl or ethyl, R representsn-propyl, isopropyl, isobutyl, sec. butyl or n-amyl, R representshydrogen or methyl, X represents hydrogen, halogen, methyl, methylthio,methylsulphinyl, methoxy, or acetyl, and n is l to 3.

The term halogen is to be understood as meaning fluorine, chlorine,and/or bromine.

Preferred compounds on account of their action are those of the formulaI wherein R represents ethyl, R represents n-propyl, R representshydrogen or methyl, X represents hydrogen, chlorine, methyl, methylthio,or methylsulphinyl, and n is l, 2, or 3.

The compounds of the formula I can be manufactured by methods that areknown per se:

acid a gg eptor I CH=HH 3 I la CH=CCH H acid aggptor (III) H R Me SH Inthe formulae 11 to X1, the symbols R R R X and n have the meanings asgiven for the formula 1 and Me represents an alkali metal, in particularsodium or potassium, ammonium or alkylammonium, and hal" represents ahalogen atom, such as fluorine, chlorine, bromine, or iodine.

Suitable acid acceptors are tertiary amines, e.g. trialkylamines,pyridine, dialkyl anilines; inorganic bases, e.g. hydrides, hydroxides,carbonates and bicarbonates of alkali metals and alkaline earth metals.

During the reactions it is sometimes necessary to use catalysts, e.g.copper or copper chloride. Processes 1a and lb, 2 and 3 are carried outat a reaction temperature between and 130C, at normal pressure, and insolvents or diluents.

Examples of suitable solvents or diluents are: ethers and etherealcompounds, e.g. diethyl ether, dipropyl ether, dioxan, tetrahydrofuran;amides, e.g. N,N- dialkylated carboxy amides; aliphatic, aromatic andhalogenated hydrocarbons, in particular benzene, toluene, xylenes,chloroform, chlorobenzene nitriles, e.g. acetronitriles; dimethylsulphoxide; ketones; e.g. acetone, methyl ethyl ketone; water. Ethanolis also suitable for process 3.

The starting materials of the formulae 11, V, and VIII can bemanufactured in analogous manner to known methods, e.g. those describedin Organic Reactions ll, pages 1 to 48. v

The compounds of the formula 1 have a broad biocidal activity and can beused for controlling a variety of plant and animal pests. Surprisingly,however, they act better against e.g. larvae of Spodoptera littoralisthan analogous compounds of German Offenlegungsschrift 2.163.391.

In addition, however, they are also suitable for controlling alldevelopment stages, e.g. eggs, larvae, pupae, nymphs, and adults ofinsects of the families: Acrididae, Blattidae, Gryllidae,Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae,Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae,Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae,Curculionidae, Tineidae, Noctuidae, Lymantriidae, Paralidae,Galleriidae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae,Trypetidae, Pulicidae, as well as Acaridae of the families: Ixodidae,Argasidae, Tetranychidae, Dermanyssidae.

By addition of other insecticides and/or acaricides it is possible toimprove substantially the insecticidal or acaricidal action and do adaptit to given circumstances.

Examples of suitable additives are: organic phosphorus compounds,nitrophenols and derivatives thereof; pyrethrines; formamidines; ureas;carbamates and chlorinated hydrocarbons.

In addition to the above mentioned properties, the compounds of theformula 1 are also active against fungi, especially against thephytopathogenic fungi belonging to the class of Basidomycetes, e.g.Piricularia oryzae. The compounds of the formula 1 are also suitable forcontrolling phypathogenic nematodes.

The compounds of the formula 1 may be used as pure active substance ortogether with suitable carriers and- /or additives. Suitable carriersand additives can be solid or liquid and correspond to the substancesconventionally used in formulation technology, for example natural orregenerated substances, solvents, disperand/or fertilisers.

For application, the comppuridsof the formula I may be processed todusts, emulsion concentrates, granules, dispersions, ,sprays, tosolutionspr suspensions, in the conventional formulation which iscommonly employed in application technology. Mention is also to be madeof cattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are manufactured in known mannerby intimately mixing and/or grinding active substances of the formula 1with the suitable carriers, optionally with the addition of dispersantsor solvents which are inert towards the active substances. The activesubstances can take, and be used in, the following forms:

Solid forms:

dusts, tracking agents, granules, coated granules, impregnated granulesand homogeneous granules. Liquid forms:

a. active substances which are dispersible in water:

wettable powders, pasts, emulsions:

b. solutions.

The content of active substance in the above described agents is between0.1 to in which connection it should be mentioned that, in the case ofapplication from aircraft or some other suitable means of application,it is possible to use concentrations of up to 99.5% or even pure activesubstance.

The active substances of the formula I can, for example, be formulatedas follows:

Dusts The following substances are used to manufacture a. a 5% and b) a2% dust:

a. 5 parts of active substance 95 parts of talcum b. 2 parts of activesubstance 1 part of highly disperse silicic acid 97 parts of talcum.

The active substances are mixed with the carriers and ground.

Granules The following substances are used to produce 5% granules:

5 parts of active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6parts of acetone; the polyethylene glycol and cetyl polyglycol ether arethen added. The resulting solution is sprayed on kaolin, and the acetoneis subsequently evaporated in vacuo.

Wettable powder:

The following constituents are used for the preparation of a) a 40%, b)and c) a 25%, and d) a 10% wettable powder:

a. 40 parts of active substance,

5 parts of sodium lignin sulphonate,

l partof sodium dibutyl-naphthalene sulphonate,

, 54 parts of silicic acid.

b. 25 parts of active substance,

4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagnechalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutyl naphthalene sulphonate,

19.5 parts of silicic acid,

19.5 parts of Champagne chalk,

28.1 parts of kaolin.

c. 25 parts of active substance,

2.5 parts of polyoxyethyleneethanol,

1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

8.3 parts of sodium aluminium silicate,

16.6 parts of kieselguhr,

46 parts of kaolin.

d. parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with theadditives, the mixture being then ground in the appropriate mills androllers. Wettable powders are obtained which can be diluted with waterto give suspensions of any desired concentration.

isoo'ctylphenoxy- Emulsifiable concentrates:

The following substances are used to produce a) a 10% and b) a 25%emulsifiable concentrate:-

a. 10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

13.4 parts of a combination emulsifier consisting of fatty alcoholpolyglycol ether and alkylaryl sulphonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene,

25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

Compounds 10 parts of an a1kylarylsulphonate/fatty alcoholglycol ethermixture,

5 parts of dimethylformamide,

57.5 parts of xylene. A

From these concentrates it is possible to produce, by dilution withwater, emulsions of any desired concentration.

Spray:

The following constituents are used to prepared a 5% spray: 9

5 parts of active substance,

1 parts of epichlorohydrin, 94 parts of benzene (boiling limits C190C).

EXAMPLE 1 O-ethyl-S-n-proplyl-O- 2-propenyl-4-methylphenylthiolphosphate (n)C 11 s :1

5 7 9-0 c. c H- 5 as a yellow oil with a refractive index of r1 1.5345.The following compounds are also manufactured in analogous manner:

Play s ice 1 Da ta Continued C 9 4 a m a I 5 t w .w 0 u 5. n m "U H M Ll l 1 l 0: O 0.. .m 2 D 2% 2 D w m m w m m u u m I n n n n 3 n L) n 3 I.z 5 7m 5 7 7d 5 7m 5 4 5 fi m v Q o H E C 3 F P C 3 H H 3 H r H r M H1 cfi w a c 0 W G J w a w c w. c w a N \Wfl d3 fN m OI 0l 0! 0 0n OI l O C1 ll 1 m 0 8 O 0 C O O C 0 J. O o O Continued Compounds Physical Data aU o- 255 so a. (n) 20 h (1) 0 1.6639 =Ci-I-CH EXAMPLE 2 Insecticidalingest poison action Cotton plants were sprayed wit a 0.05% aqueousemulsion (obtained from a 10% emulsifiable concentrate). After thecoating had dried, the cotton plants were populated with Spodopteralittoralis or Heliothis viresrens larvae L The test was carried out at24C and 60% relative humidity. In the above test, the compoundsaccording to Example 1 displayed good ingest poison action againstSpodopzera littoralis and Heliothis larvae.

EXAMPLE 3 Action against Chilo suppressalis Rice seedlings of thevariety Caloro were reared in a plastic bowl in such a way that theirroot system was matted to a disc. This was then immersed in a emulsionof the test preparation in a concentration of 800 ppm and allowed todrip off. Then 5 Chilo suppressalis lar- Lil LII

vae (L larvae) were put into the bowl, followed by the treated plants.The percentage kill of the larvae was determined 5 days later.

In this test, the compound according to Example 1 exhibited good actionagainst Chilo suppressalis.

EXAMPLE 4 Action against ticks A) Rhipicephalus bursa B) Boophilusmicroplus (larvae) Tests were carried out in each case with 20 OP-sensitive larvae using a dilution series analogous to that of test A.(The resistance refers to the tolerability of Diazinon). The compoundsaccording to Example I acted in these tests against adults and larvae ofRhipicephalus bursa and sensitive and OP-resistant larvae of Boophilusmicroplus.

EXAMPLE 5 .Acaricidal action Phaseolus vulgaris (dwarf beans) have aninfested piece of leaf from a mass culture of Tetranychus urticae placedon them 12 hours before the test for the acaricidal action. The mobilestages which have migrated are sprayed with the emulsified testpreparations from a chromatography atomiser so that the spray broth doesnot run off. The number of living and dead larvae,

adults and eggs are evaluated after 2 to 7 days under astereoscopicmicroscope and the result expressed in percentages. During the interim,the treated plants are kept in greenhouse compartments at 25C.

The compounds according to Example 1 were active in the above testagainst eggs, larvae and adults of Tetrar'lychus urticae.

EXAMPLE 6 Action against soil nematodes To test the action against soilnematodes, the active substance in the concentration of 200 ppm isapplied to, and intimately mixed with, soil infected with root gallnematodes (Meloidogyne arenaria). Immediately afterwards tomato cuttingsare planted in the thus prepared soil in one test run and after awaiting time of 8 days tomato seeds are sown in another test run.

In order to assess the nematocidal action the galls present on the rootsare counted 28 days after planting and sowing respectively. In thistest, the compounds according to Example 1 display good action againstMeloidogyne arenaria.

EXAMPLE? Action against Piricularia oryzae on Oryzae sativa Residualprotective action Rice plants were reared for 2 weeks and then sprayedwith a spraying broth 0.05% prepared from a wettable powder of theactive substance.

After 48 hours the treated plants were infected with a conidialsuspension of the fungus. The fungus infection was evaluated after 5days of incubation at 95lO0% relative humidity and 24C.

5 In these tests, the active substances according to Example 1 exhibitedgood action against Piricularia oryzae.

We claim:

I. A compound of the formula is O wherein R represents methyl or ethyl,R represents n-propyl, isopropyl, isobutyl, sec. butyl or n-amyl, Rrepresents hydrogen or methyl, X represents hydrogen, halogen or methyl,and n is l to 3.

2. A compound according to claim I, wherein R, represents ethyl, Rrepresents n-propyl, R represents hydrogen or methyl, X representshydrogen, chlorine or methyl.

,3. O-ethyl-S-n-propyl-O-[2-(2-methylvinyl)-6-

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1, whereinR1 represents ethyl, R2 represents n-propyl, R3 represents hydrogen ormethyl, X represents hydrogen, chlorine or methyl. 3.O-ethyl-S-n-propyl-O-( 2-(2-methylvinyl)-6-chlorophenyl)-thiolphosphate,according to claim
 2. 4. O-ethyl-S-n-propyl-O-(2-(2-methylvinyl)-phenyl)-thiolphosphate, according to claim
 2. 5.O-ethyl-S-n-propyl-O-(2-(2-methylvinyl)-4,6-dichlorophenyl)-thiolphosphate, according to claim2.
 6. O-ethyl-S-n-propyl-O-(2-(2-methylvinyl)-3,6-dichloro-phenyl)-thiolphosphate, according toclaim
 2. 7. O-ethyl-S-n-propyl-O-(2-(2-methylvinyl)-4-chloro-5-methyl-phenyl)-thiolphosphate, according toclaim
 2. 8. O-ethyl-S-n-propyl-O-(2-(2-methylvinyl)-3,4,6-trichlorophenyl)-thiolphosphate, according toclaim
 2. 9. O-ethyl-S-n-propyl-O-(2-(2-methylvinyl)-4-bromo-3,6-dichloro-phenyl)-thiolphosphate, accordingto claim 2.